Lubricant composition



Patented May 9, 1950 2,506,573 LUBRICANT COMPOSITION John D. Bartleson,

The Standard Oil Co corporation of Ohio Cleveland, Ohio, asslgnor to mpany, Cleveland, Ohio, I

No Drawing. Application June I, 1946, ,1 Serial No. 673,901

11 Claims. (01. 2525-32-7) This invention relates to lubricants and lubricant additives suitable for use under various conditions, including high temperatures or high pressures, or both, as for instance, use in an internal combustion engine operating at higher temperatures and in which the lubricant is in close contact with metallic surfaces, metal compounds and high temperature gases, and use as gear lubricants when surfaces must be lubricated which are subjected to high pressures.

In accordance with the invention, it has been found that oil dispersible products having highly advantageous properties as additives for lubricants may be prepared by reacting an element of the sulfur family, i. e., sulfur, selenium or tellurium, with the reaction product formed by reacting an unsaturated amine and a phosphorus sulfide at an elevated temperature.

The objects achieved in accordance with the present invention include the provision of an agent which may be useful itself as a lubricant, and which when added to lubricants will markedly inhibit corrosion, deposition of lacquer, acid and sludge formation, and other types of deterioration occurring under operating conditions; the provision of lubricating oils containing such an addition agent; the provision of a novel composition which is superior in its functions to other compositions now available and intended for this same general purpose, especially in that the corrosion is very low in an additive having the other desirable characteristics; and other objects which will be apparent as embodiments of the invention are disclosed hereinafter.

The metal or the nitrogen base derivatives formed from the above reaction products also have these desired properties.

The sulfur is preferably incorporated as a separate reaction step by adding elemental sulfur to the primary sulfide-amine reaction product, and maintaining the mass at about 200 to 300 F. for about a few minutes to several hours, and preferably about one hour. Selenium and tellurium function in much the same way as sulfur in this respect and may be incorporated similarly. Alternatively, the sulfur may be added to the metal or nitrogen base derivatives of the primary sulfide-amine reaction products.

The amount of the sulfur family element incorporated in the sulfide-amine reaction product is in the range of about 0.4 to about 2.4 gram atoms per oleflnic double bond in the amine. Even smaller amounts of sulfur show a significant improvement. The preferred amount of 2 sulfur is 0.4 gram atoms per oleflnic double bond in the amine.

To prepare a sulfide-amine starting material, from which the additive of the invention may be prepared by the reaction with an elemental element of the sulfur family, the sulfide-amine reaction may be carried out with direct admixture of the reactants, or by their admixture in the presence of a diluent which may or may not be subsequently removed. A volatile inert solvent, such as a saturated hydrocarbon boiling in the desired temperature range, may be used as a diluent which is to be subsequently removed. If a volatile solvent is used, it may be selected so as to have a boling point that will assist in controlling the temperature if the reaction is carried out under reflux conditions. Alterna tively, a heavier oil such as white oil, or a lubrieating oil of about the same properties as that to which the new composition is to be added, may be used as a diluent which is not to be removed. In a commercial embodiment of the invention, a diluent probably would not be used unless it is a mineral oil, since a diluent is not necessary.

The reaction is usually complete in four hours or less time. The reaction time is a function of the temperature, the amount of the sulfide that is to react, the subdivision of the sulfide, rate of stirring, etc.

The pentasulfide is preferred although other phosphorus sulfides or mixtures of sulfides may be employed. Phosphorus pentasulfide is most economic and readily available and for this reason is used in the illustrative examples. Under suitable conditions sulfides of arsenic or antimomr may be similarly employed.

A large variety of unsaturated amines ma: be used providing they contain at least one amine hydrogen, that is, a hydrogen attached directly to the nitrogen. The amine should contain at least one unsaturated or oleflnic double bond. Mixed amines may be used, or an amine containing different types of radicals, for example, aliphatic, aromatic, or heterocyclic at least one of which contains an olefinic double bond. Primary and secondary aliphatic unsaturated amines which have an olellnic radical of at least twelve carbon atoms are preferred i. e., monoor dioctadecenyl, octadecadienyl, hexadecenyl, hexadecadienyl, and the like unsaturated radicals containing twelve to eighteen carbon atoms. Analogous polyamines may be used.

The amine stock may be a mixture of different amines of different molecular weight and degrees 3 of substitution. Tertiary amines and other lower amines or nitrogen bases may be present.

The reaction temperature between the amine and sulfide may vary somewhat with the amine used, but in general the temperature must be elevated, i. e. at least about 250 F'., preferably above about 400 F. and desirably in the range of about 480 to 580 F., about 500 F. being particularly preferred, at atmospheric pressure. Economy of heat suggests that a temperature higher than that necessary to carry out the reaction will be wasteful. The temperature should not be so high as to decompose the reaction product, and 600 F. may be viewed as a practical economic upper limit, although much higher temperatures produce a satisfactory prodnot. The reaction time varies somewhat with the amine and the temperature and falls within the general range of from 1 minute to about hours, desirably from about to about 7 hours and preferably about hour. The reaction is somewhat exothermic and on a commercial scale the heat evolved thereby may be used to maintain the temperature. The ingredients may be added in increments if this is desirable for temperature control or for other reasons.

The sulfide-amine yield is very high in the higher temperature process. and appreciable amounts of oil insoluble products are not formed. Generally, the amount of sulfide is chosen so that it will all react at the temperature selected, and the reaction is continued until it is consumed. Associated with the high temperature treatment is the evolution of sulfur containing gas, for instance ms.

The amount of the sulfide reacted with the unsaturated amine in the reaction to make the primary reaction product used as a starting material for reaction with elemental sulfur, may vary over a wide range when the final product is to be used as such, 1. e. not as the derivative of a basic compound such as a metallic or nitrogen base. In the metal product the amount of sulfide should be more closely controlled to obtain optimum solubility of the product in oil as will be explained later. In the non-neutralized product, the amount of the sulfide may be up to 2.5 or more mols per mol of amine, and the reaction product as well as the reaction product thereof with elemental sulfur will be fully oil dispersible. The amount of the sulfide used is based upon the molar quantity of the amine without primary reference to the extent of the unsaturation in the amine. Even small amounts of phosphorous sulfide are adequate, but in general the preferred amount falls within the range of 0.3 to 1.3 mols of sulfide per mole of amine.

In making the final non-metallic or nonnitrogen base additive, the primary amine-sulfide reaction product can be reacted with elemental sulfur or a member of the sulfur family, as described previously. If desired, the final reaction product can be filtered or centrifuged. The reaction product is ready for addition to lubricating oil in the amount to achieve the desired inhibitory effect.

The sulfur-amine-sulfide additive .iust described can also be utilized in the form of the metallic or nitrogen base derivatives. Their metal derivatives may be formed from one or more metal compounds, such as their sulfides, oxides or iurdroxides. These metals may be one or more of the following: an alkali metal, such as sodium, potassium and lithium: an alkaline earth metal, such as calcium, barium, strontium;

or aluminum or other metal lower than aluminum in the electromotive series, such as zinc, lead, chromium, cobalt. antimony, arsenic. tin, copper or molybdenum. The metal should be selected with reference to the use of the composition and the properties desired in it. The alkali and alkaline earth metals have excellent detergent characteristics. The heavier metals have surface corrosion inhibition characteristics. The preferred metals are group I, group II and group III metals of the periodic table, such as potassium, zinc. barium and aluminum.

When the additive oi the invention is to be employed in the form of a metal derivative, the ratio of the sulfide to the amine entering into the amine-sulfide reaction product should be more closely controlled if optimum solubility in oil is desired. In general, this should be within the range of 0.01 to 0.55 mol of the sulfide per mol or weight unit of the hydrocarbon radical in one mol of amine, that is to say, the maximum amount of Pass for optimum dispersibility of the reaction product is about 1.1 mols of P285 per mol of a secondary amine and about 0.55 mol of P285 per mol of primary amin When a metallic or nitrogen base derivative is desired, there are two primary alternative ways of producing this:( 1) the amine-sulfide reaction product can be reacted with an element of the sulfur family and this reaction product then converted into the metal derivative, or (2) the primary amine-sulfide reaction product can be converted into the metal derivative and this derivative then reacted with an element of the sulfur family.

In the second alternative method, when a. metal derivative is to be made, the amine-sulfide reaction product can be made under temperature conditions other than the high temperature; then the metal derivative thereof can be made under the high temperature conditions; and then an element of the sulfur family can be incorporated as dlsclosed hereinbefore.

In the preparation of metal derivatives, if the primary amine-sulfide reaction product was made at or heated to the high temperatures, as described heretofore, the reaction step of forming the metal derivatives may be carried out at temperatures in the range of about to about 400 F., a. temperature in the range of about 180 to 250 F. being preferred. This reaction is also usually completed in four hours or less time, and the some factors as to reaction time are involved as discussed heretofore. Alternatively, if the primary amine-sulfide reaction product has not been subjected to the higher temperatures, the metal derivative should be prepared at or subjected to the higher temperatures as described heretofore. A diluent may be used, as described heretofore, in making the metal derivatives, but is not necessary. If a diluent is used in the amine-sulfide reaction, it can be carried over into this reaction step and be subsequently separated if desired.

From about 0.25 to about 6.0 equivalents of the metal compound may be used per mol of the sulfide in the sulfide-amine reaction product, preferably about 1.0 to about 3.0 equivalents. An equivalent is the quotient of a mol divided by the valence of the metal concerned. The metal hydroxide is generally insoluble in the aminesulfide reaction product and the amount that reacts is the amount that is no longer present as a solid phase in the reaction mass.

The reaction products obtained by reacting sulfur with the amine-sulfide reaction products may be converted to their nitrogen base derivatives by reaction with one or more basic nitrogenous compounds such as ammonia, amines, or heterocyclic nitrogenous bases. Generally, ammonia and the gaseous or liquid amines Or nitrogenous organic compounds are preferred. The organic nitrogenous bases may be one or more of the following: mono-, dior tri-alkyl, -aryl, or mixed alkyl aryl amines, wherein the alkyl or aryl groups may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, normal pentyl, a secondary pentyl, isopentyl, hexyl, cyclohexyl, phenyl, methylphenyl, a diamethylphenyl, a trimethylphenyl, or the like. The heterocyclic bases may be typified by pyridine, a lower alkyl substituted pyridine where the alkyl may be an ethyl, methyl, or propyl group, quinoline, isoquinoline, and the like. Analogous polyamines may be used similar! e. g. ethylene diamine, di-ethylene triamine, and the like.

The reaction of forming the nitrogen base derivative of the primary sulfide-amine reaction product may be carried out at room temperatures or above, depending upon the boiling point or the melting point of the nitrogenous bases used. In the case of volatile amines or ammonia, room temperature is preferred. In the case of a liquid nitrogen base, a higher temperature may be used although the temperature preferably should not be above the boiling point of the nitrogen base. For a normally solid nitrogen base, temperatures above its melting point are preferred, but the temperature should not be above the boiling point thereof. Atmospheric or elevated pressures may be used and in the case of the more volatile nitrogen bases, an elevated pressure is preferred. This reaction is also completed in four hours or less time and the same factors as to reaction time are involved as discussed heretofore. A diluent may be used as described heretofore but is not necessary. If a diluent is used in the sulfide-amine reaction, it may be carried over into this reaction step and may be subsequently separated, if desired. In general, it is preferred to prepare the primary reaction product in one step, and to prepare its nitrogen base derivative in a separate step. However, if desired, a one-step process of preparing the final product may be used.

From about 0.25 to about 6.0 equivalents of the nitrogen base may be used per mol of the sulfide in the sulfide-amine reaction product, preferably about 1 to about 4 equivalents. An equivalent is the quotient of a mol divided by the valence of the nitrogenous base concerned.

It is beneficial to have water present in the reaction step of forming the metal or the nitrogenbase derivative, and this may be introduced as water of crystallization, or as a hydrate of the metal compound or of the nitrogen base, or it may be introduced separately. A plurality of metals or of nitrogen bases, or both, may be used, 1. e., sodium and calcium, calcium and barium, calcium or zinc and aluminum or tin, ammonia, saturated or unsaturated aliphatic, naphthenic or aromatic or mixed nitrogen bases, or any one or more of the above named metals with any one or more of the above nitrogen bases. If the amount of the metal or the nitrogen base, or both, is small, the final product may be a mixture of the initial reaction product and the metal or nitrogen base derivative. The yield in the above reaction step is very high.

After this reaction step is complete, the reaction mass is processed, e. g. centrifuged or fli- .low as .01

tered, to remove water and any traces of oil insoluble by-product substances. If an excess of the basic metal compound is used, the unreacted excess may be separated at this stage. If a solvent is used as a diluent, it may be removed by vacuum distillation at this stage.

The reactions may be carried out in the absence of air or in an atmosphere of an inert gas, such as nitrogen.

Use of the additives These new compositions are lubricants and impart many desirable properties to lubricants, such as oils and greases, to which they have been added. They act as inhibitors of corrosion therein, and also as very powerful detergents and inhibitors of lacquer and sludge formation. They improve the viscosity index. They also improve the extreme pressure characteristics thereof, as well as the pour point.

The amount of the above described reaction product of sulfur with the reaction product of the phosphorus sulfide with an unsaturated amine, or its metal or nitrogen base derivative, to be added to the oil or grease will depend upon the characteristics of the oil or grease intended to be used. Some oils have more of a tendency to corrode metals, or to form acids, sludges and lacquer deposits than others, and such oils require larger quantities of the addition agent. Also, oils that are intended for higher temperatures require larger amounts of the additive. In general, for lubricating oils, the range is from 1 to 10% by weight but under some circumstances amounts as show a significant improvement. For extreme pressure lubricants the range is from 0.5 to 25.0% by weight. There is no upper limit because the additive is a lubricant but, of course, it may be uneconomical to add more than is necessary to impart to the lubricant the desired properties.

The following examples of the preparation of new compositions in accordance with the invention and tables of results of tests of lubricants comprising some of such compositions will serve to illustrate and point out some advantages of the invention, but in no wise to limit the scope thereof as otherwise disclosed and claimed herein.

Example 1 A commercially available unsaturated primary amine mixture containin about by weight of octadecenyl and octadecadienyl radicals and about 20% of hexadecenyl radicals was used in the following preparation. This amine contained about 1.25 olefinic double bonds per molecule of amine, as an overall average, and had an iodine number in the range of to 110.

270 grams of the above unsaturated amine and grams of phosphorus pentasulfide were mixed and heated at 500 F. for thirty minutes, with agitation. The reaction mass was then cooled to 300 F., 32 grams of sulfur added thereto and heating at 300 F., with agitation, continued for one hour. The resulting reaction mass was filtered hot.

Example 2 526 grams of this unsaturated amine and 222 7 grams of phosphorus pentasulnde were mixed and heated at 500 F. for thirty minutes, with agitation. The reaction mass was then cooled to 300 1"., 8 grams of sulfur added thereto, and heating at 300' I". with agitation, continued for one hour. The resulting reaction mass was filtered hot.

(a) 2'70 grams of the unsaturated amine described in Example 1 and 110 grams of phosphorus pentasulflde were mixed and heated at 500 F. for thirty minutes, with agitation. It was then cooled to 300" R, 16 grams of sulfur was added thereto and the reaction mass heated at 300 F.. with agitation, for one hour. The resulting reaction mass was filtered hot.

(b) 67.2 grams of potassium hydroxide and 130 grams of water were added to the reaction product (a), and the reaction mass agitated for one hour at 200 F. After blowing with nitrogen to remove the water, the resulting reaction mass was filtered hot.

Example 4 (a) 135 grams oi the unsaturated amine described in Example 1 and 44 grams oi. phosphorus pentasulfide were mixed and heated at 500 F. for thirty minutes, with agitation. The reaction mass was then cooled to 300 F., 8 grams of sulfur added thereto and heating at 300 R, with agitation, continued for one hour. The resulting reaction mass was filtered hot.

(b) 2'! grams of potassium hydroxide and 52 grams of water were added to the reaction product (a) and the reaction mass was agitated for one hour at 200 F. Alter blowing with nitrogen to remove the water, the resulting reaction mass was filtered hot.

In order to demonstrate the properties or the new phosphorus sulfide-amine reaction products and their derivatives in improving the characteristics oi lubricating oils, a large number of representative additives were tested according to laboratory test procedures for evaluating the service stability oi oils as described in a paper by R. E. Burk, E. C. Hughes, W. E. Scovill and J. D. Bartleson presented at the Atlantic City meeting of the American Chemical Society in September, 1041, and in another paper by the same authors presented at the New York City meeting of the American Chemical Society in September, 1944, published in- Industrial and Engineering Chemistry, Analytical dition, vol. 17, No. 5, May, 1945. P es 302-309. The latter paper also correlates the re-' sults oi such laboratory tests with the so-called standardized Chevrolet engine test."

Essentially the laboratory test equipment consists of a vertical, thermostatically heated, large glass test tube, into which is placed a piece of steel tubing 01 about one third its length and of much smaller diameter. A piece of copper-lead hearing strip is smpended within and from the upper endoi'thesteeltubebyacopperpin,andanair inlet is provided for admitting air into the lower endoithesteeltubeinsuchaway thatinrlsing theairwilicausetheoilpresenttocirculate. The test tube is filled with an amount or the oil to be tested which is at least sui'licient to submerge the metals.

The ratios of surface active metals to the volume of oil in an internal combustion test engine are nearly quantitatively duplicated in the test equipment. The rate or air fiow per volume oilisadiustedtothesameastheaverageiora test engine in operation. 0! the cata y c eiiects, those due to iron are the most important.

They are empirically duplicated by the addition 01' a soluble iron salt. Those due in lead-bromide are duplicated by its addition. In the "iron tolerance test, 0.05% oi iron salt is added. The duration of the test is adjusted to that usually used in engine type tests. As is shown by the data in the papers referred to the laboratory tests have been correlated with engine tests and the properties of the oil in an engine may be determined from the result 0! the laboratory tests. The results given in the following tables were obtained from tests using:

A 160 cubic centimeter sample of the lubricant composition liters of air per hour square centimeters of steel surface 4.4 square centimeters of copper-lead surface 1.0 square centimeters of copper surface 0.10% by weight of lead bromide powder 0.05% soluble iron calculated as FezO: (Ferric 2- ethyl hexoate in C. P. benzene) The iron tolerance" tests were run at 280 F. for 36 hours. The lacquer is deposited on the steel tube and is determined by diilerence in weight of the tube after washing with chloroform and drying to constant weight. The oil insoluble sludge remaining in the glass tube is thought to be related to similar sludge deposits in engines, and was rated visually against color photographic standards, an appearance rating scale ranging from F (worst) through A (best) being used. The corrosion was determined by diilerence in weight of the copper and heavy metal pieces after scrubbing with chloroform. The used oil was sufflcient to enable the determination of all of the usual all tests, viz. isopentane insolubles, viscosity, acid number, etc.

The data in the following table shows the reresults obtained in testing the new'additlves by the tests described.

Iron tolerance" tests on a conventional Mid- Continent acid treated lubricating oil base stock blended with Mid-Continent bright stock (8. A. E. 30), and compositions containing this oil and a high temperature phosphorous pentasulilde unsaturated amine reaction product or a derivative thereof were run on a number of the additives; the results given in the lollowlng table are representative:

Table Additive from Example No. None 1 2 a (a) 4 (u) 4 (b) Concentration of Additive in percent by weight--- 0 1.5 1.5 1.5 1.5 1.5 Lacquer Deposit (in milligrams) 39.4 0.0 0.5 5.0 1.5 9.5 Sludge (lsopentane Insoluble in milligramfiunu. 800. 2 62. I 10 22. 2 00.0 5. 2 Corrosion (in milligrams) weight oi Copperlead Bearing A]loy 0.4 1.0 0 3.1 -0.7 0.8 Acid Number A- 9.4 0.92 1.6 0.73 1.1 1.0 Viscosity Increase (BUS)--- 008 l! 43 42 i4 30 Appearance Rating. E B A+ A- A. A+

70 istic is improved. The Example 2 and Example 4(a) additives show no bearing metal corrosion (there was a slight gain in weight in the 4(a) test), and the Example 1 additive shows a nero lacquer value;

70 The eiiectiveness or the new additive was also tested by the standard Chevrolet engine test" for testing lubricating oils.

In the Chevrolet engine test, the engine is a conventional Chevrolet engine with 216.5 cu. in. piston displacement and a compression ratio of 6.5 to 1. Prior to each test new piston rings and two new copper-lead bearing inserts are installed. The engine is operated at 3150 11.. P. M. with a load of B. H. P. and at a temperature at the jacket outlet of 200 F. Besides the weight loss of the test bearings, deposits in the power section, and properties or the used oil, sampled near the middle and also at the end of the test, are examined.

It can be seen that the engine test is a slow and expensive test and that a laboratory test is the more practical way of testing a large number of samples in a relatively short time. However, an engine test was made on a solvent extracted lubricating oil containing 1% by weight of an additive of the invention, and this showed improvement as did the above laboratory test data.

The following 36 hour Chevrolet test data is illustrative of the improvement imparted to a solvent extracted Mid-Continent base lubricating oil by 1% by weight of the metal derivative product of Example 3(b) Engine rating:

Varnish rating (total) 47.5 Sludge rating (total) 44.25

Overall 91.75 Bearing corrosion, mgms./bearing hall shell 45 Used oil rating:

Viscosity increase (SUB) 165 Pentane insolubles 184 Acid number 0.52

These data are very striking. The bearing corrosion is especially low. This is particularly impressive when one keeps in mind that the base oil is one which shows a corrosion of as high as 2000 mgms./bearing half shell. The overall rating is also remarkable, an overall rating of 90 being considered very good in the art, and the used oil test shows a particularly low acid number.

In order to prevent foaming of the oil containing a small proportion of the additive, it is desirable in some cases to add a very small amount of tetra-amyl silicate, or an alkyl ortho carbonate, ortho formate or ortho acetate. 0.0003% of polyalkylsilieone oil, or 0.001% of tetra-amyl silicate was found to prevent foaming upon bubbling of air through 011 containing a few percent of the additive.

It will be obvious to one skilled in the art that reaction products of a sulfur family element with sulfide-amine reaction products, and similar products obtained by introducing phosphorus and/or sulfur into an unsaturated amine and metal or nitrogen base derivatives thereof, as prepared according to different procedures but having substantially the same properties as those herein described, may be made and used in lubricant compositions in accordance with the invention. The invention as claimed contemplates such compositions broadly except as do not come within the scope or the following claims.

I claim:

1. A lubricant comprising an oil dispersible reaction product of 1 mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one oleilnic double bond and having at least one 75 to about 600 amine hydrogen and 0.3 to 2.5 mols of aphosphorus sulfide reacted at an elevated temperature, which contains an added element of the sulfur i'amily reacted therein at a temperature in the range 01 200 to 300 F.

2. A lubricant comprising an oil dispersible reaction product of 1 mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one oleiinic double bond and having at least one amine hydrogen and 0.3 to 2.5 mols of phosphorus pentasulfide subjected to a temperature of at least 250 and below temperatures up to 600 F. at which the reaction product would be decomposed of at least 400 F. and below temperatures up to 600 F. at which the reaction product would be decomposed, which contains an added element of the sulfur family reacted therein at a temperature in the range of 200 to 300 F.

3. A lubricant comprising an oil dispersible reaction product of 1 mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one oletlnic double bond and having at least one amine hydrogen and 0.3 to 2.5 mols of phosphorus pentasulflde subjected to a. temperature of at least 400 F. and below temperature up to 600 F. at which the reaction product would be decomposed, which contains added elemental sulfur reacted glaerein at a temperature in the range of 200 to 4. A lubricant comprising an oil dispersible reaction product of 1 mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one olefinic double bond and having at least one amine hydrogen and 0.3 to 2.5 mols of phosphorus pentasulfide subjected to a temperature in the range of 400 F. to about 600 E, which contains added elemental sulfur reacted therein at a temperature in the range of 200 to 300 F.

5. A lubricant comprising an oil dispersible derivative of a reaction product of 1 mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one olefinic double bond and having at least one amine hydrogen and 0.3 to 2.5 mols or a phosphorus sulfide subjected to a temperature of at least 400 F. and below tempera.- tures up to 600 F. at which the reaction product would be decomposed, and which contains an added element of the sulfur family reacted therein at a temperature in the range of 200 to 300 F., said derivative being selected from the group consisting of a nitrogen base derivative and a metal derivative said metal being from the first three period groups.

6. A lubricant comprising an oil dispersible derivative of a reaction product of one mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one olefinic double bond and having at least one amine hydrogen and from 0.01 to 0.55 mols of phosphorus pentasulflde per mol of hydrocarbon radical in the amine subjected to a temperature in the range of 400 F. to about 600 E, which contains added elemental suliur reacted therein at a temperature in the range of 200 to 300 F., said derivative being selected from the group consisting of a nitrogen base derivative and a metal derivative said metal being from the first three period groups.

7. A lubricating oil comprising an oil dispersible potassium derivative of a reaction product of one mol of an unsaturated organic amine of 12 to 18 carbon atoms having at least one oleflnic double bond and having at least one amine hydrogen and from 0.01 to 0.55 mols of phosphorus pentasulflde per mol of hydrocarbon in the amine subjected to a temperature in the range oi 400 F., which contains added elemental 1 l sulfur reacted therein at a temperature in the range 0! 200 to 300 I".

B. A lubricating oil comprising an oil dispersible derivative of a reaction product oi. one moi of an unsaturated organic amine of 12 to 10 carbon atoms having at least one oleflnic double bond and having at least one amine hydrogen and from 0.01 to 0.55 mole of phosphorus pentasulflde per moi of hydrocarbon radical in the amine subjected to a temperature in the range of 400 to about 600 F., which contains added elemental sulfur reacted therein at a temperature in the range or 200' to 900 It, said derivative being selected iron the group consisting of a nitrogen base derivative and a metal derivative said metal being from the first three od groups.

9. A i ubricating oil comprising an oil dispersible reaction product oi one mol 0! a primary octadecenyl amine and 0.5 mol of phosphorus pentasuitlde subjected to a temperature oi 500 It, which contains 0.5 gram atoms of added elemental sulfur reacted therein at a temperature in the range of 200 to 300 F.

10. A lubricating oil comprising an oil dispersible derivative of a reaction product of one moi of a primary octadecenyl amine and 0.5 moi of phosphorus pentasuliide subjected to a temperature of 500 R, which contains 0.5 gram atoms or added elemental suli'ur reacted therein at a temperature in the range or 200' to 300 It, said derivative being selected from the group or consisting o! a nitrogen base derivative and a, metal derivative said metal being from the first three period groups.

11. A lubricating oil comprising an oil dispersible potassium derivative of a reaction product of one moi of a primary octadeceuyl amine and 0.5 moi o! phosphorus pentasulilde subjected to a temperature 0! 500 F., which contains 0.5 gram atoms of added elemental sulfur reacted therein at a temperature in the range of 200 to 300 F.

JOHN D. BARTLESON.

REFERENCES crrnn The following references are of record in the tile 0! this patent:

UNITED STATES PATENTS Number Name Date 2,146,584 Lipkin Feb. '1, 1939 2,316,087 Gaynor et a1 Apr. 6, 1943 2,403,894 Bartleson July 9, 1946 

1. A LUBRICANT COMPRISING AN OIL DISPERSIBLE REACTION PRODUCT OF 1 MOL OF AN UNSATURATED ORGANIC AMINE OF 12 TO 18 CARBON ATOMS HAVING AT LEAST ONE OLEFINIC DOUBLE BOND AND HAVING AT LEAST ONE AMINE HYDROGEN AND 0.3 TO 2.5 MOLS OF A PHOSPHORUS SULFIDE REATED AT AN ELEVATED TEMPERATURE, WHICH CONTAINS AN ADDED ELEMENT OF THE SULFUR FAMILY REACTED THEREIN AT A TEMPERATURE IN THE RANGE OF 200* TO 300*F.
 5. A LUBRICANT COMPRISING AN OIL DISPERSIBLE DERIVATIVE OF A REACTION PRODUCT OF 1 MOL OF AN UNSATURATED ORGANIC AMINE OF 12 TO 18 CARBON ATOMS HAVING AT LEAST ONE OLEFINIC DOUBLE BOND AND HAVING AT LEAST ONE AMINE HYDROGEN AND 0.3 TO 2.5 MOLS OF A PHOSPHORUS SULFIDE SUBJECTED TO A TEMPERATURE OF AT LEAST 400*F. AND BELOW TEMPERATURES UP TO 600*F. AT WHICH THE REACTION PRODUCT WOULD BE DECOMPOSED, AND WHICH CONTAINS AN ADDED ELEMENT OF THE SULFUR FAMILY REACTED THEREIN AT A TEMPERATURE IN THE RANGE OF 200* TO 300* F., SAID DERIVATIVE BEING SELECTED FROM THE GROUP CONSISTING OF A NITROGEN BASED DERIVATIVE AND A METAL DERIVATIVE SAID METAL BEING FROM THE FIRST THREE PERIOD GROUPS. 